JP7682652B2 - toner - Google Patents

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, electrostatic printing, toner jet, etc.

As copiers and printers become more widespread, the performance required of toner is becoming more advanced. In recent years, a digital printing technology called print-on-demand (POD), which prints directly without going through the plate-making process, has been attracting attention. In the POD market, there are expectations for higher speed and higher image quality than ever before.
As one of the means to achieve high image quality, a large particle size toner with high electric field followability has been proposed from the viewpoint of suppressing toner scattering to non-image areas. However, compared with a small particle size toner, a large particle size toner has a smaller deformation amount during fixing. Therefore, there are problems such as poor low-temperature fixing property to media and difficulty in high-speed printing.
In order to realize high speed printing, there is a demand for a toner with excellent low-temperature fixing property that can be efficiently fixed at a lower temperature. In order to improve the low-temperature fixing property, a material having a sharp melting property has been proposed. For example, Patent Document 1 discloses a toner using a crystalline resin with excellent low-temperature fixing property as a main binder.

JP 2019-207400 A JP 2015-059947 A

The crystalline resin described in Patent Document 1 has a side chain of a hydrocarbon-based unit in the molecule. Therefore, the hydrocarbon units between the molecules are oriented to each other, and the sharp melting property is expressed by having a crystalline portion. However, since the molecular chains are less entangled in the crystalline portion, it is considered that the hardness and tenacity of the toner containing the above resin are low. When the toner containing the above resin is printed and the surface of the printed matter is rubbed, a problem such as the toner set-off may occur.
As a means for reducing the stress caused by friction and suppressing the offset of the toner, a method of exposing a lubricating material on the image surface can be mentioned. For example, Patent Document 2 discloses a toner that reduces offset by exposing a lubricating material on the image surface and reducing the stress applied to the image surface. However, when the lubricating material is exposed on the image surface, the fixing member may be contaminated during fixing.
The present invention has been made in consideration of the above-mentioned problems, and provides a toner that does not contaminate components and has excellent developability, low-temperature fixability, and abrasion resistance.

The present invention provides a toner having toner particles containing a binder resin and a hydrocarbon wax,
The binder resin contains a crystalline resin,
the crystalline resin has a weight average molecular weight of tetrahydrofuran soluble matter of 200,000 or more and 1,000,000 or less as measured by gel permeation chromatography ;
The crystalline resin satisfies the following requirement (I) or (II):
(I):
(I-i) a first monomer unit represented by the following formula (1), and
(I-ii) A second monomer unit selected from the group consisting of an acrylonitrile unit, a methacrylonitrile unit, a vinyl acetate unit, and an acrylic acid unit.
having
(I-iii) the sum of the first monomer unit and the second monomer unit is 100 mass% based on the total mass of all monomer units of the crystalline resin;
(II):
(II-i) a first monomer unit represented by the following formula (1):
(II-ii) a second monomer unit selected from the group consisting of an acrylonitrile unit, a methacrylonitrile unit, a vinyl acetate unit, and an acrylic acid unit; and
(II-iii) A third monomer unit which is a styrene unit
having
(II-iv) the total of the first monomer unit, the second monomer unit and the third monomer unit is 100% by mass based on the total mass of all monomer units of the crystalline resin;
a ratio of the first monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
a ratio of the second monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
The hydrocarbon wax has a carboxylic acid group and an acid value of 5 mgKOH/g or more and 50 mgKOH/g or less.
The present invention relates to a toner characterized by the above-mentioned.

（式（１）中、
Ｒ_Z1は、水素原子又はメチル基を表し、Ｒ¹は、炭素数１８以上３６以下の直鎖アルキル基を表す。）

(In formula (1),
_R represents a hydrogen atom or a methyl group, ^{and R} represents a linear alkyl group having 18 to 36 carbon atoms.

The present invention provides a toner that has excellent developability, low-temperature fixability, and abrasion resistance without contaminating components.

In the present invention, the expressions "xx or more and xx or less" or "xx to xx" that express a numerical range refer to a numerical range including the lower and upper limit endpoints, unless otherwise specified.

In the present invention, (meth)acrylic acid ester means an acrylic acid ester and/or a methacrylic acid ester.

In the present invention, a "monomer unit" refers to one section of carbon-carbon bonds in the main chain of a polymer formed by polymerization of a vinyl monomer. A vinyl monomer can be represented by the following formula (Z).

［式（Ｚ）中、Ｒ_Z1は、水素原子、又はアルキル基（好ましくは炭素数１以上３以下のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_Z2は、任意の置換基を表す。］

[In formula (Z), _R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and _R represents an arbitrary substituent.]

A crystalline resin is a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurements.

The following describes in detail how to implement the present invention.

The present invention provides a toner having toner particles containing a binder resin and a hydrocarbon wax,
The binder resin contains a crystalline resin,
The crystalline resin is
The weight average molecular weight is 200,000 or more and 1,000,000 or less,
(i) a first monomer unit represented by the following formula (1), and (ii) a second monomer unit represented by the following formula (2) or (3) which is different from the first monomer unit,
a ratio of the first monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
a ratio of the second monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
The hydrocarbon wax has an acid value of 5 mgKOH/g or more and 50 mgKOH/g or less.
It is characterized by the above.

（式（１）中、Ｒ_Z1は、水素原子又はメチル基を表し、Ｒ¹は、炭素数１８以上３６以下のアルキル基を表す。）

(In formula (1), _R represents a hydrogen atom or a methyl group, and ^R represents an alkyl group having 18 to 36 carbon atoms.)

（式（２）中、Ｘは単結合又は炭素数１以上６以下のアルキレン基を示し、
Ｒ³は、－Ｃ≡Ｎ、－Ｃ（＝Ｏ）ＮＨＲ¹⁰（Ｒ¹⁰は水素原子、又は炭素数１以上４以下のアルキル基を表す。）、ヒドロキシ基、－ＣＯＯＲ³¹（Ｒ³¹は炭素数１以上６以下のアルキル基、炭素数１以上６以下のヒドロキシアルキル基、又は水素原子を表す。）、－ＮＨ－Ｃ（＝Ｏ）－Ｎ（Ｒ³³）₂（Ｒ³³はそれぞれ独立して、水素原子又は炭素数１以上６以下のアルキル基を表す。）、－ＣＯＯ（ＣＨ₂）₂ＮＨＣＯＯＲ³⁴（Ｒ³⁴は炭素数１以上４以下のアルキル基を表す。）、又は－ＣＯＯ（ＣＨ₂）₂－ＮＨ－Ｃ（＝Ｏ）－Ｎ（Ｒ³⁵）₂（Ｒ³⁵はそれぞれ独立して、水素原子又は炭素数１以上６以下のアルキル基を表す。）を表し、
Ｒ⁴は、水素原子又はメチル基を表す。）

In formula (2), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ³ represents -C≡N, -C(=O)NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms), a hydroxy group, -COOR ³¹ (R ³¹ represents an alkyl group having from 1 to 6 carbon atoms, a hydroxyalkyl group having from 1 to 6 carbon atoms, or a hydrogen atom), -NH-C(=O)-N(R ³³ ) ₂ (each R ³³ independently represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms), -COO(CH ₂ ) ₂ NHCOOR ³⁴ (R ³⁴ represents an alkyl group having from 1 to 4 carbon atoms), or -COO(CH ₂ ) ₂ -NH-C(=O)-N(R ³⁵ ) ₂ (each R ³⁵ independently represents a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms);
^R4 represents a hydrogen atom or a methyl group.

（式（３）中、Ｒ⁵は、炭素数１以上４以下のアルキル基を表し、
Ｒ⁶は、水素原子又はメチル基を表す。）

In formula (3), R ⁵ represents an alkyl group having 1 to 4 carbon atoms,
^R6 represents a hydrogen atom or a methyl group.

As a result of intensive research, the inventors discovered that the above problem could be solved by controlling the composition and ratio of the monomer units of the crystalline resin and the acid value of the wax within specific ranges, and thus arrived at the present invention. The inventors speculate that the reason for solving the above problem is as follows.

Resins that have hydrocarbon-based units in the side chains of their molecules have crystallinity. This is thought to be because the hydrocarbon units between the molecules are oriented with each other, creating crystalline sites. Therefore, resins that have hydrocarbon-based units in the side chains have sharp melting properties and exhibit good low-temperature fixing properties.

However, since the molecular chains are less entangled in the crystalline parts, it is believed that the resin has less hardness and toughness. When printing with a toner containing the above-mentioned crystalline resin, friction occurring on the image surface of the printed material can cause problems such as the toner bleeding through to the other side.

On the other hand, if the entanglement of molecular chains is improved in order to increase the hardness and toughness of the resin, the resin's crystallinity will be compromised, leading to a deterioration in low-temperature fixability.

Therefore, in order to improve abrasion resistance without compromising low-temperature fixability, it is necessary to increase the entanglement of molecules while maintaining crystallinity, thereby increasing the strength of the resin.

The inventors have discovered that by making a toner by adding a hydrocarbon wax having an acid value to a crystalline resin having a polar group, it is possible to increase the strength of the toner particles while maintaining the sharp melting properties derived from the crystalline resin, and to achieve both low-temperature fixing properties and abrasion resistance. After detailed investigation, it was found that the effect is influenced by the fact that the crystalline resin in the toner particles has a polar group and the hydrocarbon wax has an acid value, which led to the present invention.

Hydrocarbon waxes with acid values have carboxylic acid groups in their molecules. The carboxylic acid of the hydrocarbon wax with acid values in the toner particles and the polar groups in the main chain of the crystalline resin create a dipole-dipole interaction. It is believed that the hydrocarbon wax with acid values acts as a bridge between the molecules of the crystalline resin, attracting them together. It is therefore assumed that this improves the tenacity and elasticity of the toner particles.

In addition, the hydrocarbon wax with an acid value interacts with the polar groups of the crystalline resin, and does not inhibit the crystal formation of the crystalline resin side chains. It is speculated that the crystalline resin efficiently forms crystals because the side chains of the crystalline resin are oriented to avoid the hydrocarbon wax with an acid value.

As a result, the toner particles have sharp melting properties derived from the crystalline resin, and the resin strength derived from the cohesiveness between the molecules is improved.

Therefore, we believe that the toner of the present invention can achieve both low-temperature fixability and abrasion resistance.

In addition, because the hydrocarbon wax having an acid value interacts with the crystalline resin, excessive migration to the image surface during fixing is reduced. As a result, it is believed that the toner of the present invention is less likely to cause member contamination, such as migration of the hydrocarbon wax having an acid value in the toner to the fixing member during fixing.

In addition, the hydrocarbon wax with an acid value strongly interacts with the polar groups of the crystalline resin, and is therefore uniformly dispersed within the toner particles. As a result, the hydrocarbon wax with an acid value is not unevenly distributed locally on the toner surface, which is thought to reduce the adhesive force of the toner particles and improve fluidity.

Therefore, we believe that the toner of the present invention does not aggregate during development and has good dot reproducibility.

The toner of the present invention contains a binder resin having a crystalline resin and a wax.

<Crystalline Resin>
The crystalline resin of the present invention has a weight average molecular weight (Mw) of tetrahydrofuran (THF) soluble matter measured by gel permeation chromatography (GPC) of 200,000 to 1,000,000, preferably 220,000 to 300,000. When the weight average molecular weight of the crystalline resin is within the above range, the polar group of the crystalline resin that interacts with the wax having an acid value is present in an appropriate amount, thereby improving the resin strength. In addition, the wax having an acid group does not inhibit the crystallinity of the resin due to the interaction between the polar group of the crystalline resin and the wax having an acid group, so that excellent low-temperature fixing properties can be obtained. In addition, the wax is less likely to be exposed to the toner surface, the adhesion force of the toner base is reduced, and the fluidity of the toner is improved. In addition, excessive exposure of the wax to the image surface is reduced during toner fixing, and contamination of the member is reduced.

Therefore, the toner of the present invention has good low-temperature fixing properties, suppression of component contamination, abrasion resistance, and dot reproducibility.

The crystalline resin of the present invention has a first monomer unit represented by the above formula (1). The first monomer unit represented by the above formula (1) is derived from a first polymerizable monomer which is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.

When the first monomer unit is a (meth)acrylic acid ester having an alkyl group with 18 to 36 carbon atoms, crystallinity can be imparted to the resin. This allows the toner to exhibit sharp melting properties and provide excellent low-temperature fixability.

Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontane (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].

Among these, from the viewpoint of low-temperature fixability, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms is preferred, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms is more preferred, and linear behenyl (meth)acrylate is even more preferred.

The polymerizable monomer derived from the first monomer unit represented by the above formula (1) may be used alone or in combination of two or more kinds.

The crystalline resin of the present invention has a second monomer unit represented by the above formula (2) or (3) that is different from the first monomer unit. By including the second monomer unit, crystallization of the first monomer unit is promoted, and the resin has excellent low-temperature fixing properties.

The reason for this is thought to be as follows. Specifically, the first monomer unit is incorporated into the crystalline resin, and crystallinity is expressed by the aggregation of the first monomer units. In general, the crystallization of the first monomer unit is inhibited when other monomer units are incorporated. As a result, it becomes difficult for the first monomer unit to express crystallinity as a crystalline resin. This tendency becomes more pronounced when multiple types of monomer units are randomly bonded together within the molecule of the crystalline resin.

However, when a first monomer unit and a second monomer unit with a higher polarity than the first monomer unit are used together as constituent monomers of a crystalline resin, it is believed that the first monomer units can be bonded in a moderate amount of continuity during polymerization of the crystalline resin. Because crystalline resins tend to have a structure similar to that of a block copolymer, crystallinity can be enhanced even when other monomer units are incorporated.

Therefore, the toner of the present invention has good low-temperature fixing properties derived from the crystalline portion of the crystalline resin. Furthermore, the high polarity portion of the crystalline resin improves the resin strength through interaction with the wax having an acid value, and has good abrasion resistance.

Specific examples of the second monomer unit that can be used include polymerizable monomers that satisfy the above formula (2) or (3) among the polymerizable monomers listed below.

Monomers having nitrile groups; for example, acrylonitrile, methacrylonitrile, etc.

Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, acrylic acid, etc.

Monomers having an amide group; for example, acrylamide, a monomer obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method.

Monomers having a urea group; for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms (primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cycloxylamine, etc.) with an isocyanate having 2 to 30 carbon atoms and an ethylenically unsaturated bond by a known method.

Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.

Among these, it is preferable to use a monomer having a nitrile group, an amide group, a hydroxy group, or a urea group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, and a urea group, and an ethylenically unsaturated bond. Acrylonitrile, methacrylonitrile, and acrylic acid are particularly preferable.

Also preferably used as the second monomer unit are vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate. Among these, vinyl esters are preferred from the viewpoint of low-temperature fixability, since they are non-conjugated monomers and therefore tend to maintain a suitable reactivity with the first polymerizable monomer and tend to increase the crystallinity of the polymer.

The proportion of the first monomer unit in the crystalline resin of the present invention is 20.0% by mass or more and 70.0% by mass or less, and preferably 30.0% by mass or more and 60.0% by mass or less, based on the total mass of all monomer units in the crystalline resin.

When the ratio of the first monomer unit is within the above range, the resin has crystallinity and the toner exhibits sharp melting properties, resulting in excellent low-temperature fixability. In addition, the polar group derived from the second monomer unit is present, and the resin strength is appropriately improved by interaction with the wax having an acid group. Furthermore, the exposure of the wax to the toner surface is reduced, and the adhesive force of the toner base is reduced. This improves the fluidity of the toner. Furthermore, excessive exposure of the wax to the image surface during toner fixing is reduced, resulting in less contamination of the components.

As a result, the toner of the present invention has good low-temperature fixing properties, suppression of component contamination, abrasion resistance, and dot reproducibility.

The proportion of the second monomer unit is 20.0% by mass or more and 70.0% by mass or less.

When the proportion of the second monomer unit is within the above range, an interaction occurs between the polar group of the crystalline resin and the wax having an acid group, and the strength of the resin is appropriately improved. In addition, due to the interaction between the polar group of the crystalline resin and the wax having an acid group, the wax having an acid group does not inhibit the crystallinity of the resin, and excellent low-temperature fixing properties are obtained. In addition, the wax is less likely to be exposed to the toner surface, the adhesive force of the toner base is reduced, and the fluidity of the toner is improved. In addition, excessive exposure of the wax to the image surface is reduced during toner fixing, and contamination of the member is reduced.

As a result, the toner of the present invention has good low-temperature fixing properties, suppression of component contamination, abrasion resistance, and dot reproducibility.

In addition, when the crystalline resin has monomer units derived from two or more types of (meth)acrylic acid esters having alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit represents the mass ratio of the total of them.

The crystalline resin of the present invention may contain a third monomer unit derived from a third polymerizable monomer, as long as the mass ratio of the first monomer unit and the second monomer unit described above is not impaired. For example, the following monomers can also be used.

Styrene and its derivatives such as styrene and o-methylstyrene, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among these, it is preferable that the third polymerizable monomer is styrene. When it is styrene, the aromatic ring of styrene causes π-π interactions between molecules, improving the strength of the toner particles. This is preferable because it reduces the adhesion force of the toner particles and improves dot reproducibility.

The proportion of the third monomer unit is preferably 5.0% by mass or more and 40.0% by mass or less, more preferably 10.0% by mass or more and 20.0% by mass or less, based on the total mass of all monomer units in the crystalline resin.

The melting point of the crystalline resin is preferably 50°C or higher and 80°C or lower, and more preferably 53°C or higher and 70°C or lower. When the melting point of the crystalline resin is within the above range, it exhibits better low-temperature fixing properties. The melting point of the crystalline resin can be adjusted by the type and amount of the first polymerizable monomer and the type and amount of the second polymerizable monomer used.

<Softening point of crystalline resin>
The softening point of the crystalline resin is preferably from 70° C. to 115° C., and more preferably from 100° C. to 120° C. When the softening point is within the above-mentioned range, the wax of the present invention described above can be prevented from being excessively present on the image surface during image formation, and low-temperature fixability and abrasion resistance of the printed matter can be achieved at the same time.

The crystalline resin is preferably a vinyl polymer. Examples of vinyl polymers include polymers of monomers containing ethylenically unsaturated bonds. Ethylenically unsaturated bonds refer to carbon-carbon double bonds capable of radical polymerization, and examples of such groups include vinyl groups, propenyl groups, acryloyl groups, and methacryloyl groups.

<Hydrocarbon wax>
The wax having an acid value of the present invention has a main skeleton of a hydrocarbon chain, and is generally called a hydrocarbon wax, to which an acid group has been introduced through a modification process. Examples of the modified hydrocarbon wax will be described below, together with the production method.

For example, a manufacturing method includes polymerizing paraffin wax, polyolefin wax, microcrystalline wax, Fischer-Tropsch wax, etc. using a Ziegler catalyst, and after the polymerization is completed, oxidizing it to produce an alkoxide of the catalyst metal and polyethylene, which is then hydrolyzed.

Another example is a production method in which a hydrocarbon wax is oxidized in the liquid phase with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. A mixture of boric acid and boric anhydride, or metaboric acid and pyroboric acid can also be used as a catalyst.

Other examples include boron oxyacids, phosphorus oxyacids, and sulfur oxyacids. Specific examples include boric acid, nitric acid, phosphoric acid, and sulfuric acid. As the molecular oxygen-containing gas to be blown into the reaction system, a wide range of oxygen, air, or a mixture of these diluted with an inert gas can be used. The liquid phase oxidation reaction is usually carried out without using a solvent, while the raw material hydrocarbon wax is in a molten state. The reaction temperature is 120 to 280°C, preferably 150 to 250°C. The reaction time is preferably 1 to 15 hours.

The acid value of the wax of the present invention is 5 mgKOH/g or more and 50 mgKOH/g or less. Preferably, it is 20 mgKOH/g or more and 40 mgKOH/g or less.

When the acid value of the wax is within the above range, the polar group derived from the second monomer unit and the wax having an acid group effectively interact with each other and do not inhibit the crystallinity of the resin, resulting in excellent low-temperature fixability. In addition, the interaction between the polar group derived from the second monomer unit and the wax having an acid group moderately improves the strength of the resin. Furthermore, the exposure of the wax to the toner surface is reduced, and the adhesive force of the toner matrix is reduced. This improves the fluidity of the toner. Furthermore, excessive exposure of the wax to the image surface during toner fixing is reduced, resulting in less contamination of the components.

Therefore, when the acid value of the wax is within the above-mentioned range, the low-temperature fixability, suppression of component contamination, abrasion resistance, and dot reproducibility are good.

The wax having an acid value used in the present invention preferably has a maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC) when the crystalline structure made of hydrocarbon chains melts, which is 80°C or more and 150°C or less. More preferably, it is 90°C or more and 140°C or less. If the maximum endothermic peak temperature and acid value are within the above-mentioned ranges, it is possible to achieve both suppression of component contamination and abrasion resistance of the printed matter.

The content of the wax having an acid value of the present invention is preferably 1.0 parts by mass or more and 20.0 parts by mass or less relative to 100 parts by mass of the binder resin. More preferably, it is 1.0 parts by mass or more and 16.0 parts by mass or less, and even more preferably, it is 5.0 parts by mass or more and 12.0 parts by mass or less. When the content of the wax having an acid value is within the above range, it is possible to achieve both suppression of component contamination and abrasion resistance of the printed matter.

<Other resins>
The binder resin of the toner of the present invention may contain a resin other than the crystalline resin, if necessary.

Examples of resins other than the crystalline resin used in the binder resin of the toner of the present invention include the following resins. Homopolymers of styrene and its substitutes, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.

Among these, styrene copolymers and polyester resins are preferred. Also, it is preferable that they are amorphous.

The binder resin contains amorphous polyester. The amorphous polyester has a softening point of 85°C or more and 105°C or less, and preferably 90°C or more and 100°C or less.

It is preferable that the amorphous resin has at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols condensed at its terminal.

The amorphous resin preferably contains an amorphous polyester resin containing a bisphenol derivative and ethylene glycol as alcohol components of the polyester resin. The content ratio of the bisphenol derivative to ethylene glycol is preferably 2.0 to 6.0, more preferably 3.0 to 5.0, in terms of mol% of the bisphenol derivative/mol% of ethylene glycol. When the content ratio of the bisphenol derivative to ethylene glycol is within the above range, the steric hindrance of the polyester resin molecules is reduced.

Here, when molecular motion is active, the wax with an acid value interacts with the polar groups of the crystalline resin, acting as a bridge between the crystalline resin molecules. The polyester resin molecules can penetrate between the crystalline resin molecules due to the small steric hindrance of the ethylene glycol portion. In this case, the ester bonds of the polyester resin molecules and the acid groups at the molecular ends interact with the polar portions of the crystalline resin molecules. In the process of crystallizing the wax with an acid value, the main chain of the crystalline resin and the ester bonds and acid portions at the molecular ends of the polyester resin molecules are incorporated into the crystalline portions of the wax.

As a result, the strength of the toner particles is increased and their abrasion resistance is improved. The presence of ethylene glycol in the molecules of the amorphous polyester resin increases the concentration of ester groups per molecule, which is thought to be why the above effects are more pronounced.

The amorphous resin of the present invention preferably contains an amorphous polyester resin condensed with at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols having a specific number of carbon atoms.

The aliphatic compound introduced into the polyester resin is preferably at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols. The carbon number of the aliphatic compound (the average carbon number of the aliphatic compound) is preferably 30 or more and 80 or less, more preferably 30 or more and 60 or less.

The aliphatic compound is preferably monovalent. By being monovalent, the aliphatic compound is condensed to the molecular end of the amorphous polyester resin. The carbon chain derived from the aliphatic compound condensed to the molecular end has affinity with the wax having an acid value, and an interaction is effectively expressed.

Specifically, the wax with an acid value acts as a bridge between the molecules of the crystalline resin. When the polar sites of the crystalline resin molecule and the polar sites of the wax with an acid value interact with each other, the aliphatic hydrocarbon sites bonded to the ends of the molecules of the amorphous polyester resin have an affinity for the wax with an acid value and can penetrate between the molecules of the crystalline resin. At that time, the ester bond of the amorphous polyester resin molecule approaches the polar sites of the crystalline resin molecule, and an interaction occurs.

As a result, it is believed that the strength of the toner particles will increase and their abrasion resistance will improve.

The amount of the aliphatic compound added is preferably 0.10 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.10 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the total mass of the monomers constituting the polyester resin into which the aliphatic compound is condensed. By adding an amount of the aliphatic compound within the above range, it is possible to effectively express an interaction with a wax having an acid value without inhibiting the crystallization of the wax having an acid value.

The aliphatic compound used in the present invention is not particularly limited as long as it is an aliphatic monocarboxylic acid or an aliphatic monoalcohol having a specific chain length. For example, any of primary, secondary, and tertiary compounds can be used. Specific examples of aliphatic monocarboxylic acids include melissic acid, lactoseric acid, tetracontanoic acid, and pentacontanoic acid. Examples of aliphatic monoalcohols include melissic alcohol and tetracontanol.

There is no particular limitation on the method for condensing an aliphatic compound to the terminal of a polyester resin. In a preferred embodiment, when producing a polyester resin, an aliphatic compound is added simultaneously to the monomers that make up the polyester resin, and condensation polymerization is carried out. This allows the aliphatic compound to be condensed more uniformly to the terminal of the polyester resin.

In the present invention, the method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the above-mentioned divalent carboxylic acid compound and divalent alcohol compound are charged simultaneously with an aliphatic monocarboxylic acid or an aliphatic monoalcohol, and polymerized through an esterification reaction or an ester exchange reaction and a condensation reaction to produce a polyester resin. The polymerization temperature when producing the polyester resin is not particularly limited, but is preferably in the range of 180°C to 290°C. For the polymerization of the polyester unit, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. In particular, it is more preferable that the binder resin in the present invention contains a polyester unit polymerized using a titanium-based catalyst. The use of a titanium-based catalyst improves the charging uniformity in the toner.

Specific examples of titanium compounds include titanium diisopropylate bistriethanol aminate [Ti( _C6H14O3N ) ₂ ( _C3H7O ) ₂ ], titanium diisopropylate bisdiethanol aminate [ _Ti ( _{C4H10O2N ) 2 ( C3H7O} )2], titanium dipentylate bistriethanol aminate [Ti( _C6H14O3N ) ₂ ( _C5H11O ) ₂ ], titanium diethylate bistriethanol aminate [ _{Ti (C6H14O3N ) 2} ( _C2H5O ) _{2 ]} , titanium dihydroxyoctylate bistriethanol aminate _[ Ti( _{C6H14O3N ) 2 ( C2H5O} ) _{2 ] , titanium} diisopropyl _... ( _OHC8H16O ) ₂ ], titanium distearate bis(triethanol aminate) [Ti( _C6H14O3N ) ₂ ( _C18H37O ) ₂ ], titanium triisopropylate triethanol aminate [ _{Ti(C6H14O3N)1(C3H7O)3], titanium monopropylate tris(triethanol aminate) [Ti(C6H14O3N ) 3 ( C3H7O ) 1 ] , etc. Among these , titanium diisopropylate} bis(triethanol aminate ₎ , titanium diisopropylate bis( _diethanol aminate) and titanium dipentylate bis(triethanol aminate) _are preferred.

Specific examples of other titanium catalysts include tetra-n-butyl titanate [Ti(C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti(C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti(C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti(C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti(C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti(C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti(C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ], and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate, and dioctyl dihydroxyoctyl titanate are preferred. These can be obtained, for example, by reacting titanium halide with the corresponding alcohol. In addition, it is more preferred that the titanium compound contains an aromatic carboxylic acid titanium compound. It is preferred that the aromatic carboxylic acid titanium compound is obtained by reacting an aromatic carboxylic acid with a titanium alkoxide. In addition, the aromatic carboxylic acid is preferably a divalent or higher aromatic carboxylic acid (i.e., an aromatic carboxylic acid having two or more carboxyl groups) and/or an aromatic oxycarboxylic acid. Examples of the divalent or higher aromatic carboxylic acid include dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or their anhydrides, polyvalent carboxylic acids such as trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, and naphthalene tetracarboxylic acid, or their anhydrides, esters, and the like. In addition, examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, and tropic acid. Among these, it is more preferable to use a divalent or higher carboxylic acid as the aromatic carboxylic acid, and it is particularly preferable to use isophthalic acid, terephthalic acid, trimellitic acid or naphthalenedicarboxylic acid.

<Inorganic fine particles>
The toner of the present invention may be a conductive toner or an insulating toner. The toner of the present invention may contain inorganic fine particles as necessary. The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner as an external additive.

In the case of conductive toner, examples of inorganic fine particles include fine particles such as carbon black, silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles thereof. Among inorganic particles, carbon black and silica fine particles are preferred for improving flowability and making conductivity uniform. The volume resistivity (Ω·cm) of the conductive toner is preferably 1.0×10 ⁶ or more and 3.0×10 ⁶ or less.

In the case of insulating toner, examples of inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles of these. Among inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging.

The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

From the viewpoint of improving fluidity, the inorganic fine particles as an external additive preferably have a specific surface area of 50 ^m2 /g or more and 400 ^m2 /g or less. From the viewpoint of improving durability and stability, the inorganic fine particles as an external additive preferably have a specific surface area of 10 ^m2 /g or more and 50 ^m2 /g or less. In order to achieve both improved fluidity and durability and stability, inorganic fine particles having a specific surface area in the above range may be used in combination.

The content of the external additive is preferably 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of the toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

<Coloring Agent>
The toner of the present invention may be a magnetic toner or a non-magnetic toner.

When the toner of the present invention is used as a non-magnetic toner, carbon black or any other conventionally known pigment or dye may be used as a colorant as necessary. The amount of colorant added is preferably 0.1 parts by mass or more and 100.0 parts by mass or less, more preferably 0.5 parts by mass or more and 95.0 parts by mass or less, relative to 100.0 parts by mass of the binder resin.

When the toner of the present invention is used as a magnetic toner, magnetic iron oxide particles can be used. Specific examples of the magnetic iron oxide particles include magnetite, maghemite, ferrite, and other magnetic iron oxide particles containing other metal oxides. Conventionally, iron oxide black (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (Cd ₃ Fe ₂ O ₄ ), gadolinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), manganese iron oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (Fe), etc. Particularly suitable magnetic iron oxide particles are fine powders of iron tetroxide or gamma ferric oxide. The above-mentioned magnetic iron oxide particles can be used alone or in combination of two or more kinds.

The shape of the magnetic iron oxide particles used in the toner of the present invention is preferably an octahedron, which has better dispersibility in the toner and is more likely to exhibit a filler effect.

<Toner particle size>
The toner of the present invention is not particularly limited in particle size, but larger particles are more effective in high-speed printing. The weight average particle size (D4) of the toner is preferably 10.0 μm or more and 20.0 μm or less, and more preferably 12.0 μm or more and 18.0 μm or less. When the toner particle size is in the above-mentioned range, the electric field tracking property is improved, and the dot reproducibility is improved.

<Softening Point of Toner>
The softening point of the toner of the present invention is preferably from 70° C. to 130° C., and more preferably from 100° C. to 120° C. When the softening point is within the above-mentioned range, the above-mentioned wax of the present invention can be prevented from being excessive on the image surface during image formation, and low-temperature fixability and abrasion resistance of printed matter can be achieved at the same time.

<Toner Manufacturing Method>
The method for producing the toner of the present invention is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used.

The procedure for producing toner using the pulverization method is explained below.

In the raw material mixing process, materials constituting the toner particles, such as binder resin, wax, colorant, and other components such as charge control agent if necessary, are weighed out in predetermined amounts, blended, and mixed. Examples of mixing devices include a double con mixer, V-type mixer, drum type mixer, super mixer, Henschel mixer, Nauta mixer, and Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

Next, the mixed materials are melt-kneaded to disperse the wax in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, and single-screw or twin-screw extruders are the mainstream due to their advantage of continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Co-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with a twin roll or the like and cooled with water in a cooling process.

The cooled resin composition is then pulverized to the desired particle size in a pulverization process. In the pulverization process, the resin composition is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further pulverized using a pulverizer such as a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), a Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), a Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.), or an air jet type pulverizer.

Then, if necessary, the mixture is classified using a classifier or sieve such as an inertial classification system such as Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification system such as Turboplex (manufactured by Hosokawa Micron Corporation), TSP Separator (manufactured by Hosokawa Micron Corporation), or Faculty (manufactured by Hosokawa Micron Corporation).

If necessary, an external additive is added to the surface of the toner particles. Methods for adding an external additive include blending the classified toner with a predetermined amount of various known external additives, and stirring and mixing the resulting mixture using a mixing device such as a double con mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

The methods for measuring various physical properties of toner particles and raw materials are explained below.

<Method of separating each material from toner>
By utilizing the difference in solubility of each material contained in the toner in a solvent, each material can be separated from the toner.
First separation: Toner (crystalline resin, wax, colorant, inorganic fine particles, etc.) is dissolved in methyl ethyl ketone (MEK) at 100° C., and the soluble matter (crystalline resin, wax) and insoluble matter (colorant, inorganic fine particles, etc.) are separated.
Second separation: The soluble matter (crystalline resin, wax) obtained in the first separation is dissolved in chloroform at 23° C., and the soluble matter (crystalline resin) and the insoluble matter (wax) are separated.

<Method for measuring the proportion of monomer units derived from various polymerizable monomers in a crystalline resin>
The content of monomer units derived from various polymerizable monomers in the crystalline resin is measured by ¹ H-NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10,500 Hz
Number of measurements: 64 Measurement temperature: 30°C
Sample: 50 mg of a measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a thermostatic chamber at 40° C. to prepare a sample.

From the obtained ^1H -NMR chart, for example, in the case of a polymer, a peak independent of peaks attributable to components of monomer units derived from the first polymerizable monomer is selected, and an integral value _S1 of this peak is calculated.

Similarly, from the peaks attributable to the components of the monomer unit derived from the second polymerizable monomer, a peak independent of the peaks attributable to the components of the monomer units derived from the other monomer units is selected, and the integral value _S2 of this peak is calculated.

Furthermore, in the case where a third polymerizable monomer is used, a peak independent of the peaks attributable to the constituent elements of the monomer unit derived from the third polymerizable monomer is selected from the peaks attributable to the constituent elements of the monomer unit derived from the other monomer units, and the integral value _S3 of this peak is calculated.

The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the above integral values _S1 , _S2 , and _S3 , where _n1 , n2 _{, and n3} are the numbers of hydrogen atoms in the constituent elements to which the peaks of interest for each site belong.

Content (mol %) of monomer unit derived from first polymerizable monomer=
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Similarly, the content ratios of the monomer units derived from the second polymerizable monomer and the third polymerizable monomer are determined as follows.

Content (mol %) of monomer unit derived from second polymerizable monomer=
{(S ₂ /n ₂ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Content (mol%) of monomer unit derived from third polymerizable monomer=
{(S ₃ /n ₃ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100

In the case where the polymer contains a polymerizable monomer that does not contain hydrogen atoms in any of its constituent elements other than the vinyl group, the measurement is performed in single pulse mode using ^13C -NMR with ^13C as the measurement nucleus, and the calculation is performed in the same manner using ^1H -NMR.

<Measurement of Wax Acid Value>
The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of a sample. The acid value is measured in accordance with JIS K 0070-1992 as follows.

(1) Preparation of Reagents 1.0 g of phenolphthalein was dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water was added to make 100 mL to obtain a phenolphthalein solution.

Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, from the amount of potassium hydroxide solution required for neutralization. The 0.1 mol/L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

(2) Procedure (A) Main test 2.0 g of the crushed sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene/ethanol (2:1) is added and dissolved over 5 hours. Next, several drops of the above phenolphthalein solution are added as an indicator, and titration is performed using the above potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.

(B) Blank Test: A titration is carried out in the same manner as above, except that no sample is used (i.e., only a mixed solution of toluene/ethanol (2:1) is used).

(3) The obtained result is substituted into the following formula to calculate the acid value.
A=[(CB)×f×5.61]/S
Here, A is the acid value (mg KOH/g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

<Method for measuring the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of a crystalline resin>
<Method for measuring the peak top temperature of the endothermic peak measured by differential scanning calorimetry (DSC) of wax>
The peak top temperature of the endothermic peak of the crystalline resin measured by differential scanning calorimetry (DSC) and the peak top temperature of the endothermic peak of the wax measured by differential scanning calorimetry (DSC) are measured in accordance with ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).

The melting points of indium and zinc are used to correct the temperature of the device's detection section, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, about 3 mg of a sample is precisely weighed and placed in an aluminum pan, and measurement is performed under the following conditions using an empty aluminum pan as a reference.
Heating rate: 10° C./min
Measurement start temperature: 30℃
Measurement end temperature: 180°C

Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C/min. The temperature is raised to 180°C once and held for 10 minutes, then cooled to 30°C, and then heated again. During this second heating process, the peak top temperatures of the crystalline resin and wax are calculated from the temperature-endothermic curve in the temperature range of 30°C to 150°C.

<Softening points of crystalline resin, binder resin, and toner>
The softening points of the crystalline resin, binder resin, and toner are measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual that comes with the device.

In this device, a constant load is applied from above the measurement sample using a piston, while the measurement sample filled in a cylinder is heated and melted, and the molten measurement sample is extruded from a die at the bottom of the cylinder, obtaining a flow curve that shows the relationship between the amount of piston descent and temperature.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "Flow characteristic evaluation device Flow Tester CFT-500D." The melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts (this is called X. X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston descent amount on the flow curve is the sum of X and Smin is the melting temperature in the 1/2 method.

The measurement sample was prepared by compressing 1.0 g of binder resin at approximately 10 MPa for approximately 60 seconds using a tablet compression machine (NT-100H, manufactured by NPA Systems) in an environment of 25°C, and forming it into a cylindrical shape with a diameter of approximately 8 mm.

The measurement conditions for CFT-500D are as follows.
Test mode: Heating method Starting temperature: 30°C
Achieved temperature: 200℃
Measurement interval: 1.0°C
Heating rate: 4.0° C./min
Piston cross-sectional area: 1.000 ^cm2
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheat time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

<Measurement of Weight Average Particle Size (D4) of Toner>
The weight average particle diameter (D4) of the toner is measured with an effective measurement channel number of 25,000 channels using a precision particle size distribution measuring device using a capillary electrical resistance method equipped with a 100 μm aperture tube, “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated.

The electrolyte solution used for the measurements is one in which special grade sodium chloride is dissolved in ion-exchanged water to give a concentration of approximately 1% by mass, for example "ISOTON II" (manufactured by Beckman Coulter).

Before performing measurements and analysis, configure the dedicated software as follows:

In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the threshold/noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Pour about 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker for use with the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 rotations per second. Then, remove dirt and air bubbles from inside the aperture tube using the "aperture flush" function of the dedicated software.
(2) Approximately 30 mL of the aqueous electrolyte solution is placed in a 100-mL flat-bottom glass beaker, and approximately 0.3 mL of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, having a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added thereto as a dispersant.
(3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees and an electrical output of 120 W, and about 2 mL of the Contaminon N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized.
(5) In a state where the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10°C or higher and 40°C or lower.
(6) The electrolytic solution (5) in which the toner is dispersed is dropped using a pipette into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to about 5%. Then, the measurement is continued until the number of particles measured reaches 50,000.
(7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph/Volume %, the "Average diameter" on the Analysis/Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

The basic configuration and features of the present invention have been described above. The present invention will now be described in detail with reference to examples. However, the present invention is not limited to these examples.

<Production Example of Crystalline Resin 1>
Solvent: Toluene 100.0 parts by mass Monomer composition 100.0 parts by mass (The monomer composition is a mixture of behenyl acrylate, acrylonitrile, and styrene in the ratio shown below.)
Behenyl acrylate (first polymerizable monomer): 50.00 parts by mass; acrylonitrile (second polymerizable monomer): 35.00 parts by mass; styrene (third polymerizable monomer): 15.00 parts by mass; polymerization initiator t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corp.): 0.5 parts by mass. The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70° C. while stirring at 200 rpm, and a polymerization reaction was carried out for 20 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. The solution was then cooled to 24° C., and then charged into 1000.0 parts by mass of methanol while stirring, to precipitate the methanol insoluble matter. The obtained methanol insoluble matter was filtered off, washed with methanol, and vacuum dried at 40° C. for 24 hours to obtain a crystalline resin 1. The weight average molecular weight of the crystalline resin 1 was 263,700, and the peak top temperature of the temperature-endothermic curve was 61°C.

<Production Examples of Crystalline Resins 2 to 17>
Crystalline resins 2 to 17 were obtained by carrying out the reaction in the same manner as in the production example of crystalline resin 1, except that the polymerizable monomers and the parts thereof were changed as shown in Table 1.

表１中の略号は以下の通り。
ＢＥＡ：ベヘニルアクリレート（Ｒ¹炭素数２２）
ＭＹＡ：ミリシルアクリレート（Ｒ¹炭素数３０）
ＯＡ：オクタコサアクリレート（Ｒ¹炭素数２８）
ＳＡ：ステアリルアクリレート（Ｒ¹炭素数１８）
ＡＮ：アクリロニトリル
ＭＮ：メタクリロニトリル
ＶＡ：酢酸ビニル
ＡＡ：アクリル酸
Ｓｔ：スチレン

The abbreviations in Table 1 are as follows.
BEA: Behenyl acrylate ( ^R1 carbon number 22)
MYA: Myrisil acrylate (R ¹ carbon number 30)
OA: Octacosaacrylate ( ^R1 carbon number 28)
SA: Stearyl acrylate (R ¹ carbon number 18)
AN: acrylonitrile MN: methacrylonitrile VA: vinyl acetate AA: acrylic acid St: styrene

<Production Example of Wax 1>
Aliphatic hydrocarbon wax: 100 mol parts; Mixture of boric acid and boric anhydride (mol parts of boric acid/mol parts of boric anhydride = 1.5): 2 mol parts. The above aliphatic hydrocarbon wax (maximum endothermic peak temperature 125.1°C) was melted at a container temperature of 200°C, and the above mixture of boric acid and boric anhydride was added, and the wax was oxidized in _O2 / _N2 gas with an oxygen concentration of 5% by volume. The oxidation treatment time was adjusted so as to obtain a desired acid value. After the oxidation treatment was completed, water was added and purification was performed to obtain wax 1 having an acid value. The acid value of wax 1 was 30 mgKOH/g, and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC) was 130°C.

<Production Examples of Waxes 2 to 6>
Waxes 2 to 6 were obtained by carrying out the reaction in the same manner as in the production example of Wax 1, except that the acid value and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC) were changed to those shown in Table 2.

<Production Example of Amorphous Resin 1>
Monomers constituting the polyester unit used in producing the amorphous resin 1 are listed below.
Bisphenol A ethylene oxide (2.2 mol adduct): 40.0 mol parts Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts Ethylene glycol: 20.0 mol parts Terephthalic acid: 100.0 mol parts First, the above monomer was charged in a 5-liter autoclave together with 0.2 parts by mass of titanium tetrabutoxide so that 95 parts by mass of the monomers constituting the polyester unit and 50 carbon atoms of aliphatic monoalcohol (secondary monoalcohol having a hydroxyl group in paraffin wax, average carbon number 50) were charged in a 5-liter autoclave so that 5 parts by mass of the monomers constituting the polyester unit were charged in a total amount of 100 parts by mass of the monomers constituting the polyester unit. A reflux condenser, a water separator, an _N2 gas inlet tube, a thermometer and an agitator were attached thereto, and a polycondensation reaction was carried out at 230 ° C. while introducing _N2 gas into the autoclave. In addition, when carrying out the reaction, the reaction time was adjusted so as to obtain the desired softening point. After the reaction was completed, the resin was taken out of the vessel, cooled and pulverized to obtain amorphous resin 1.

<Production Examples of Amorphous Resins 2 to 7>
Amorphous resins 2 to 7 were obtained by carrying out the reaction in the same manner as in the production example of amorphous resin 1, except that the polymerizable monomers and the parts thereof were changed as shown in Table 3.

<Production Example of Magnetic Iron Oxide Particles 1>
(First reaction step)
A ferrous salt suspension was prepared by mixing 16 L of an aqueous solution of ferrous sulfate containing 1.5 mol/L of Fe2 ⁺ (Fe2 ⁺ 24 mol) with 15.2 L of a 3.0 N sodium hydroxide solution (equivalent to 0.95 equivalent to Fe2 ⁺ , i.e., 2OH/Fe=0.95) and adjusting the pH to 8.3. In this case, 26.6 g of No. ₃ water glass (SiO2 28.8 mass%) (equivalent to 0.50 atomic % of Si relative to Fe, i.e., Si/Fe (atomic %)=0.50) was diluted with 0.5 L of ion-exchanged water as a silicon component and added to the sodium hydroxide. The above ferrous salt suspension was aerated at a temperature of 90°C with 70 L of air per minute to carry out an oxidation reaction until the oxidation reaction rate of the ferrous salt reached 12%, and a ferrous salt suspension containing magnetite nucleus particles was obtained.

(Second reaction step)
A suitable amount of 3.0 N sodium hydroxide solution was added to the ferrous salt suspension containing the magnetite nucleus particles to adjust the pH to 10.5, and 70 L of air was passed through it at a temperature of 90° C. at a rate of 70 L per minute to obtain magnetic iron oxide core particle precursor 1.

(Third reaction step + coating treatment)
To the suspension containing magnetic iron oxide core particle precursor 1, appropriate amounts of No. 3 water glass as the silicon component and 1.9 mol/L aluminum sulfate solution as the aluminum component were added so that the Si/Fe and Al/Fe ratios became the values shown in Table 4. Dilute sulfuric acid was further added to adjust the pH to 5.8 and the temperature of the suspension to 90° C. to form a coating layer, thereby obtaining magnetic iron oxide 1.

The obtained magnetic iron oxide 1 was washed with water using a filter press. After washing, the electrical conductivity was 40 mS. It was then filtered, dried, and pulverized by conventional methods. The obtained magnetic iron oxide 1 contained 8% spherical magnetic iron oxide particles and 92% octahedral magnetic iron oxide particles, and had a number-average particle diameter of 0.14 μm.

Tables 4 and 5 show the preparation conditions and composition values of magnetic iron oxide 1.

<Production Example of Magnetic Iron Oxide Particles 2>
In the manufacturing example of magnetic iron oxide 1, the manufacturing conditions were adjusted as shown in Table 4 to obtain magnetic iron oxide particles 2. The composition values of the obtained magnetic iron oxide particles 2 are shown in Table 5.

Example 1 (Production of Toner 1)
Crystalline resin 1 60.0 parts by mass Amorphous resin 1 32.0 parts by mass Wax 1 8.0 parts by mass Magnetic iron oxide particles 1 100.0 parts by mass The raw materials shown in the recipe were mixed using a Henschel mixer (FM75J type, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 20 s ^-1 for a rotation time of 5 min, and then kneaded using a twin-screw kneader (TEM-26SS type, manufactured by Toshiba Machine Co., Ltd.) set at a temperature of 140°C and a barrel rotation speed of 250 rpm. The kneaded product obtained was cooled and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed product. The coarsely crushed product obtained was finely crushed using a mechanical crusher (T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.

100.0 parts by mass of the obtained toner particles 1 were mixed with 2.0 parts by mass of hydrophobic silica (BET: 200 ^m2 /g) in a Henschel mixer (FM75J type, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s ^-1 for a rotation time of 5 min, and passed through an ultrasonic vibration sieve with a mesh size of 54 μm to obtain toner 1.

[Examples 2 to 25 (production of toners 2 to 25), Comparative Examples 1 to 7 (production of toners 26 to 32)]
Toners 2 to 32 were obtained in the same manner as in Example 1, except that the types and amounts of the crystalline resin, amorphous resin, wax and magnetic iron oxide were changed to those shown in Table 6.

The obtained toners 1 to 32 were used to carry out the following various evaluations, and the results are shown in Table 7. For each evaluation, a commercially available copying machine was modified to increase the process speed, and the applicability to high-speed printing was confirmed.

[Evaluation of Low-Temperature Fixability]
For this evaluation, a commercially available digital copier (Image Press 1135, manufactured by Canon Inc.) was taken out of its fixing device, and an evaluation machine was used in which the fixing roller temperature could be set arbitrarily and the process speed was modified to 1000 mm/s. The evaluation was performed under a room temperature and humidity (23°C, 50% RH) environment. 157 g/ ^m2 paper (GF-C157, A4) was used as the evaluation paper. The development bias of the Image Press 1135 was set so that the image density was 1.2, and 9 sheets of solid black unfixed images were output. Next, the temperature control of the fixing device was changed from 80°C to 120°C in 5°C increments, and one sheet was passed at each temperature. The fixed image was cut out to a width of 45 mm x 210 mm, folded in half from the center of the long side so that the image part was on the inside, and a load of 150 g/ ^cm2 (14.7 kPa) was applied. The density after rubbing the folded portion with a brush was measured and compared with the density before folding. The image density was measured using an X-Rite color reflection densitometer (X-rite 500 Series, manufactured by X-rite Corporation). The density after folding was divided by the density before folding, and the value was plotted against each fixing temperature to create an approximation curve. The temperature at which the density after folding divided by the density before folding was 0.95 or more was determined as the fixable temperature.

(Evaluation Criteria)
A: The fixable temperature is less than 95°C.
B: The fixing start temperature is 95° C. or higher and lower than 100° C.
C: The fixing start temperature is 100° C. or higher and lower than 105° C.
D: The fixing start temperature is 105° C. or higher and lower than 110° C.
E: The fixing start temperature is 110° C. or higher.

[Evaluation of Abrasion Resistance (Scratch Resistance) of Printed Images]
For this evaluation, an evaluation machine was used in which a commercially available digital copier (Image Press 1135, manufactured by Canon Inc.) was modified to have a process speed of 1000 mm/s and a fixing temperature of 120°C. 157 g/ ^m2 paper (GF-C157, A4) was used as the evaluation paper. A solid black image was output by setting the development bias so that the image density was 1.0. Using a friction and wear tester Tribogear TYPE 40 manufactured by Shinto Scientific Co., Ltd., the output image was rubbed with unused evaluation paper while applying a load, and the amount of toner attached to the rubbed paper was evaluated. The rubbing conditions were as follows:
Weight: 500g
Contact area with the rubbing paper: 2 mm x 20 mm
Sliding speed: 1000mm/min Sliding distance: 40mm

The amount of toner adhering to the rubbing paper was evaluated as follows. Using an optical microscope, multiple photographs were taken at 100x magnification to include the entire rubbing area. The photographed images were binarized using image processing to calculate the area ratio of the adhering area. The average value of the area ratio of the adhering area for all photographs was taken as the amount of toner adhering.

(Evaluation Criteria)
A: The adhesion area rate is less than 1.5%.
B: The adhesion area rate is 1.5% or more and less than 2.5%.
C: The adhesion area rate is 2.5% or more and less than 3.5%.
D: The adhesion area rate is 3.5% or more and less than 4.0%.
E: The adhesion area rate is 4.0% or more.

[Evaluation of component contamination suppression]
For this evaluation, a commercially available digital copier (Image Press 1135, manufactured by Canon Inc.) was used, which was modified by setting the process speed to 1000 mm/s, the fixing temperature to 120° C., and removing the cleaning mechanism of the fixing roller. 157 g/m ² paper (GF-C157, A4) was used as the evaluation paper. The development bias was set so that the image density was 1.0, and a pattern with a width of 45 mm was output in the short axis direction of the A4 paper, and 5000 images were output under a high temperature and high humidity (30° C., 80% RH) environment. After that, the fixing roller was removed, and the amount of wax attached on the fixing roller corresponding to the image pattern was evaluated using a Fourier transform infrared spectroscopic analyzer. The details of the evaluation method are described below.
Fourier transform infrared spectrometer: Spectrum One (manufactured by PerkinElmer)
Measurement mode: ATR method Incident angle of infrared light (λ = 5 μm): 45°
ATR crystal: Ge (refractive index: 4.0)
Measurement range: 4000 cm ^-1 to 600 cm ^-1
Acquisition wavelength width: 4.00cm ^-1
Number of times accumulated: 16

The infrared absorption spectrum obtained under the above conditions is subjected to baseline correction using Automatic Correction. The maximum peak intensity in the range of 2800 cm ^-1 to 2900 cm ^-1 , which is the absorption peak derived from the methylene of the hydrocarbon wax, is calculated (Wp). The average value of the absorption intensities at 1100 cm ^-1 and 1250 cm ^-1 , which are peaks derived from the surface layer material of the fixing roller, is calculated (Bp). The value of Wp/Bp was taken as the amount of wax attached.

(Evaluation Criteria)
A: Wp/Bp is less than 0.01%.
B: Wp/Bp is 0.01% or more and less than 0.02%.
C: Wp/Bp is 0.02% or more and less than 0.04%.
D: Wp/Bp is 0.04% or more and less than 0.08%.
E: Wp/Bp is 0.08% or more

[Evaluation of developability (dot reproducibility)]
For this evaluation, a commercially available digital copier (image RUNNER ADVANCE 8105 PRO manufactured by Canon Inc.) was used as an evaluation machine with a process speed modified to 600 mm/s. After 100,000 sheets were printed using each magnetic toner under a high temperature and high humidity (30°C, 80% RH) environment, a halftone (30H) image was formed and the roughness of this image was evaluated based on the following criteria. The paper used was CS-068 A4 paper (basis weight 68.0 g/ ^m2 , sold by Canon Marketing Japan Inc.). The 30H image is a halftone image in which 256 gradations are expressed in hexadecimal, with 00H being solid white (non-image) and FFH being solid black (full image). The images were taken using a digital microscope VHX-500 (lens wide range zoom lens VH-Z100 manufactured by Keyence Corporation), and the area of 1000 dots was measured. The number average (S) of the dot area and the standard deviation (σ) of the dot area were calculated, and the dot reproducibility index was calculated using the following formula.
Dot reproducibility index (I) = σ/S × 100

(Evaluation Criteria)
A: I is less than 2.0 B: I is 2.0 or more and less than 4.0 C: I is 4.0 or more and less than 6.0 D: I is 6.0 or more and less than 8.0 E: I is 8.0 or more

Claims (4)

A toner having toner particles containing a binder resin and a hydrocarbon wax,
The binder resin contains a crystalline resin,
the crystalline resin has a weight average molecular weight of tetrahydrofuran soluble matter of 200,000 or more and 1,000,000 or less as measured by gel permeation chromatography ;
The crystalline resin satisfies the following requirement (I) or (II):
(I):
(I-i) a first monomer unit represented by the following formula (1), and
(I-ii) A second monomer unit selected from the group consisting of an acrylonitrile unit, a methacrylonitrile unit, a vinyl acetate unit, and an acrylic acid unit.
having
(I-iii) the sum of the first monomer unit and the second monomer unit is 100 mass% based on the total mass of all monomer units of the crystalline resin;
(II):
(II-i) a first monomer unit represented by the following formula (1):
(II-ii) a second monomer unit selected from the group consisting of an acrylonitrile unit, a methacrylonitrile unit, a vinyl acetate unit, and an acrylic acid unit; and
(II-iii) A third monomer unit which is a styrene unit
having
(II-iv) the total of the first monomer unit, the second monomer unit and the third monomer unit is 100% by mass based on the total mass of all monomer units of the crystalline resin;
a ratio of the first monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
a ratio of the second monomer unit in the crystalline resin to the total mass of all monomer units in the crystalline resin is 20.0 mass% or more and 70.0 mass% or less,
The hydrocarbon wax has a carboxylic acid group and an acid value of 5 mgKOH/g or more and 50 mgKOH/g or less.
A toner characterized by:

(In formula (1),
_R represents a hydrogen atom or a methyl group, ^{and R} represents a linear alkyl group having 18 to 36 carbon atoms. 2. The toner according to claim 1 , wherein the content of the hydrocarbon wax contained in the toner particles is from 1.0 part by mass to 20.0 parts by mass with respect to 100 parts by mass of the binder resin. 3. The toner of claim 1 or 2 , wherein said first monomer unit is behenyl acrylate. The binder resin includes an amorphous polyester,
The amorphous polyester is
(i) a softening point of 85° C. or higher and 105° C. or lower;
4. The toner according to claim 1 , wherein (ii) at least one aliphatic compound selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols is condensed at the terminal of the toner.